WO2017119343A1 - Composition for polyurethane foam - Google Patents

Composition for polyurethane foam Download PDF

Info

Publication number
WO2017119343A1
WO2017119343A1 PCT/JP2016/088725 JP2016088725W WO2017119343A1 WO 2017119343 A1 WO2017119343 A1 WO 2017119343A1 JP 2016088725 W JP2016088725 W JP 2016088725W WO 2017119343 A1 WO2017119343 A1 WO 2017119343A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane foam
polyol
composition
toner
tolylene diisocyanate
Prior art date
Application number
PCT/JP2016/088725
Other languages
French (fr)
Japanese (ja)
Inventor
彩 平田
慎也 神▲崎▼
Original Assignee
株式会社ブリヂストン
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社ブリヂストン filed Critical 株式会社ブリヂストン
Priority to EP16883842.3A priority Critical patent/EP3401345B1/en
Priority to US16/067,891 priority patent/US20200262963A1/en
Priority to CN201680078086.7A priority patent/CN108473656A/en
Publication of WO2017119343A1 publication Critical patent/WO2017119343A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G03G15/06—Apparatus for electrographic processes using a charge pattern for developing
    • G03G15/08—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints

Definitions

  • the present invention relates to a polyurethane foam composition, and more particularly to a toner seal material formed by foaming a polyurethane foam composition to form a polyurethane foam.
  • Polyurethane foam has flexible mechanical properties and is excellent in workability, so it is used as various sealing materials such as toner sealing materials and water-proof sealing materials.
  • a member using polyurethane foam is used as a member for various purposes such as charging, development, transfer, toner supply, and cleaning. Attention has been paid.
  • Such a member using polyurethane foam is used in the form of a member for an image forming apparatus having elasticity such as a charging roller, a developing roller, a transfer roller, a toner supply roller, and a cleaning roller.
  • a uniformly charged image carrier is selectively exposed to form a latent image, the latent image is visualized with toner, and the formed toner image is recorded on a recording medium.
  • the image is recorded by transferring the image onto the image.
  • toner must be replenished in a timely manner.
  • a toner cartridge in which an image carrier, a charging device, a developing device, a cleaning device and the like are integrated is used.
  • the toner can be replenished or the image carrier that has reached the end of its life can be replaced, and maintenance is easy.
  • This process cartridge system is used in many image forming apparatuses. However, if toner leaks, an image defect occurs. Therefore, a resin such as a gap between the cartridge body frames and a gap between the developing sleeve of the developing device and the developing frame body is used. A toner seal material is interposed on the contact surface of the molded product. In addition, a toner sealant is interposed on the end portion side of the image carrier so that the waste toner does not leak into the gap between the end portion of the image carrier of the cleaning device and the waste toner holder.
  • roller member As an internal member of an image forming apparatus using polyurethane foam having excellent sealing properties, it can be attached to the periphery of a toner containing portion, an image forming body, etc.
  • a toner sealing material that functions to prevent leakage and diffusion of toner.
  • a polyurethane foam used for a toner seal material is required to have a low air permeability and a fine cell structure.
  • Patent Document 1 discloses a toner seal material obtained by foaming a polyurethane foam raw material containing a polyol, an isocyanate, a catalyst, and a foam stabilizer.
  • the polyol is a dimer acid polyol
  • the ratio of diphenylmethane diisocyanate in the isocyanate is 55 to 75% by mass
  • the catalyst contains a reactive amine
  • the polyurethane foam raw material is based on 100 parts by mass of the polyol.
  • a toner seal material comprising the reactive amine in an amount of 0.2 to 0.5 parts by mass and the foam stabilizer in an amount of 3 to 5 parts by mass.
  • the air permeability was lowered and the toner sealability was excellent.
  • the problem to be solved by the present invention is to achieve excellent restoration by increasing the tensile strength of polyurethane foam and reducing the compression residual strain and hysteresis loss rate while ensuring the excellent toner sealability of polyurethane foam.
  • An object of the present invention is to provide a polyurethane foam composition capable of enjoying the properties.
  • a polyurethane foam composition comprising a polyol, tolylene diisocyanate, a foaming agent, a foam stabilizer and a crosslinking agent, the composition of the polyol, the composition of tolylene diisocyanate and the crosslinking agent. It was found that the above-mentioned problems can be solved by limiting the functionality of. The present invention has been completed based on such findings.
  • a composition comprising a polyol composed of a polyester polyol and a polyether polyol, a tolylene diisocyanate, a foaming agent, and a foam stabilizer, the polyester polyol containing a phthalate ester polyol, A composition for polyurethane foam, wherein the compositional mass ratio (2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate) is (65/35) to (70/30).
  • a toner sealing material formed from a polyurethane foam obtained by foaming the polyurethane foam composition according to [1].
  • the present invention it is possible to increase the tensile strength of the polyurethane foam while ensuring the excellent toner sealability of the polyurethane foam, and to reduce the compression residual strain and the hysteresis loss rate.
  • the composition for polyurethane foam which can exhibit property can be provided.
  • FIG. 5 is a schematic view showing a state in which a polyurethane foam sample is punched out to a length of 10 mm ⁇ 10 mm width and a toner is put inside and assembled in a compressed state of 50% between two acrylic plates in a toner sealing property measuring method.
  • FIG. 3 is a schematic view showing that the erosion degree of the toner is measured by measuring the length of the portion where the toner is eroded at six locations shown in FIG.
  • a to B representing numerical limitation means a numerical range including A and B as end points.
  • a mass part and mass% are synonymous with a weight part and weight%, respectively.
  • a combination of preferred embodiments is a more preferred embodiment.
  • the composition for polyurethane foam of the present invention is a composition comprising a polyol composed of polyester polyol and polyether polyol, tolylene diisocyanate, a foaming agent and a foam stabilizer, and the polyester polyol contains a phthalate ester polyol.
  • the compositional mass ratio of tolylene diisocyanate (2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate) is (65/35) to (70/30).
  • the polyurethane foam composition contains a polyol, and the polyol comprises a polyester polyol and a polyether polyol.
  • the polyol contained in the polyurethane foam composition of the present invention preferably has a mass ratio of polyester polyol to polyether polyol (polyester polyol / polyether polyol) of (70/30) to (30/70), The mass ratio is more preferably (60/40) to (40/60), and the mass ratio is particularly preferably (50/50). It is preferable that the mass ratio of the polyester polyol and the polyether polyol is the above because a urethane foam having both tensile strength and restorability can be obtained.
  • the amount of the polyester polyol does not exceed the mass ratio (70/30), a polyurethane foam having a good restorability is obtained. If the amount of the polyester polyol is not less than the mass ratio (30/70), the high elongation is high. It is preferable because a strong polyurethane foam can be obtained.
  • the polyester polyol includes a phthalate ester polyol.
  • the tensile strength and elongation at break of the polyurethane foam are increased by hydrogen bonds between the ester bonds of the phthalate ester polyol.
  • the effect of miniaturizing the cells of the polyurethane foam is also achieved. From this viewpoint, it is preferable that the total amount of the polyester polyol according to the present invention is a phthalate ester polyol.
  • the phthalate ester polyol according to the present invention is not particularly limited, but is selected from phthalic anhydride (o-phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid) and derivatives thereof.
  • Polyester polyols based on at least one phthalate ester polyol are preferred.
  • the main component is at least one selected from phthalic anhydride (o-phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid) and derivatives thereof in the total amount of polyester polyol.
  • a phthalate ester polyol 50% by mass or more of a phthalate ester polyol is contained, preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more. It means that.
  • the hydroxyl value of the phthalate ester polyol according to the present invention is preferably 50.0 to 65.0 mg-KOH / g, more preferably 54.0 to 58.0 mg-KOH / g.
  • the phthalate ester polyol may be used alone or in combination of two or more.
  • polyester polyol used in addition to the phthalic ester polyol for example, an aliphatic dicarboxylic acid having 3 to 20 carbon atoms such as malonic acid, succinic acid, adipic acid, suberic acid, sebacic acid, and brassylic acid, other than phthalic acid
  • polyester polyols obtained by polycondensation of these aromatic dicarboxylic acids and the like with aliphatic glycols having 1 to 6 carbon atoms such as ethylene glycol, diethylene glycol and propylene glycol.
  • polyether polyol Although it does not specifically limit as a polyether polyol in this invention, The polyether polyol obtained by the ring-opening polymerization of alkylene oxide from a reactive viewpoint is suitable. Examples of such alkylene oxides include propylene oxide (PO) and ethylene oxide (EO). These may be used alone or in combination of two or more. As the polyether polyol, the PO homopolymer, the EO homopolymer, and the polyether polyol obtained by copolymerization of PO and EO can be used. The copolymerization may be random copolymerization or block copolymerization. Examples of the polymerization initiator include pentaerythritol, glycerin, ethylenediamine, Mannich, tolylenediamine, and sucrose. These polymerization initiators may be used alone or in combination of two or more.
  • tolylene diisocyanate is used as the isocyanate compound, and it is preferable to use only tolylene diisocyanate as the isocyanate compound.
  • the compositional mass ratio (2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate) of tolylene diisocyanate needs to be (65/35) to (70/30). When the composition mass ratio is within this range, the polyurethane foam exhibits high elongation and high strength, and at the same time, the restorability is improved.
  • the amount of 2,6-tolylene diisocyanate is not smaller than the compositional mass ratio (70/30) of tolylene diisocyanate, it is preferable because stable foamability can be maintained. If the amount of tolylene diisocyanate is not increased, the cells of the obtained polyurethane foam can be miniaturized, and good sealing performance can be secured, which is preferable.
  • (2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate) is (less than 65 / more than 35)
  • the foaming rate and the resinification rate are affected by the molecular structure of 2,6-tolylene diisocyanate. The balance is lost, and the number of urethane foam cells is less than 50/25 mm.
  • the isocyanate index (isocyanate index) of tolylene diisocyanate may be 100 or less or more than 100, but is preferably 90 to 110. If the isocyanate index is within this range, the resulting foam has an appropriate hardness and is excellent in mechanical properties such as compression residual strain.
  • the isocyanate index represents the equivalent ratio of the isocyanate group of the polyisocyanate to the active hydrogen group of water such as polyol and foaming agent, expressed as a percentage. Accordingly, an isocyanate index exceeding 100 means that the polyisocyanate is in excess of the polyol or the like.
  • the polyurethane foam composition of the present invention contains a foaming agent.
  • the foaming agent is for foaming a polyurethane resin to form a polyurethane foam.
  • the foaming agent preferably contains water, and more preferably the foaming agent consists only of water.
  • the blending amount of water is preferably 2.5 to 5.0 parts by mass with respect to 100 parts by mass of the polyol. When the blending amount of water is within the above range, foaming due to foaming reaction occurs moderately, and a toner seal material having a low density can be obtained.
  • the composition for producing a polyurethane foam of the present invention contains a foam stabilizer.
  • the foam stabilizer is used as necessary in order to smoothly advance foaming performed by the foaming agent.
  • a foam stabilizer what is normally used when manufacturing a flexible polyurethane foam can be used.
  • Specific examples of the foam stabilizer include silicone compounds, anionic surfactants such as sodium dodecylbenzenesulfonate and sodium lauryl sulfate, polyether siloxane, and phenolic compounds.
  • the silicone compound has a high foam regulating power, makes the cells of the polyurethane foam fine, and lowers the air permeability. Therefore, the silicone compound is suitably used as a silicone foam regulating agent.
  • the blending amount of the foam stabilizer is preferably 1.0 to 5.0 parts by weight, more preferably 1.0 to 4.5 parts by weight, and more preferably 3.5 to More preferably, it is 4.5 parts by mass.
  • a foam foam that exhibits a sufficient foam regulating action during foaming of the foam raw material and exhibits good toner sealability with fine cells and low airflow is obtained. It is done.
  • the foam regulating action is appropriate, and a polyurethane foam having a desired communication cell can be obtained while ensuring foamability.
  • the polyurethane foam composition preferably contains a reactive silicone foam stabilizer.
  • the reactive silicone foam stabilizer By blending the reactive silicone foam stabilizer, the silicone reacts with the isocyanate or polyol and is incorporated into the bond, making it difficult to volatilize.
  • the reactive silicone foam stabilizer (sometimes abbreviated as “reactive silicone”) is at least selected from the group consisting of an amino group, an epoxy group, a hydroxyl group, a mercapto group, and a carboxy group.
  • the reactive silicone foam stabilizer is composed of an amino group, an epoxy group, a hydroxyl group, a mercapto group, and carboxy at the side chain or main chain terminal of a silicone compound such as dimethyl silicone, methyl phenyl silicone, or methyl hydrogen silicone. It is preferably selected from a reactive group selected from the group or a compound into which a group having the reactive group is introduced. Among these, a reactive silicone having a hydroxyl group or a carboxy group as a reactive group is more preferable, and a reactive silicone having a carboxy group is still more preferable.
  • the reactive silicone foam stabilizer commercially available products may be used, and various reactive silicones manufactured by various companies such as Shin-Etsu Silicone Co., Ltd., Toray Dow Corning, Momentive Performance Materials, Specifically, examples of the reactive silicone having a carboxy group include CF1218 (manufactured by Toray Dow Corning) and X22-3701 (manufactured by Shin-Etsu Silicone Co., Ltd.). Examples of the reactive silicone having a hydroxyl group include SF 8427, BY 16-201, SF 8428 (above, manufactured by Toray Dow Corning), X-22-4039, X-22-4015 (above, Shin-Etsu Silicone Co., Ltd.) Manufactured).
  • the polyurethane foam composition may contain non-reactive silicone in addition to the reactive silicone, or may use only the non-reactive silicone without using the reactive silicone.
  • the non-reactive silicone is not particularly limited as long as it does not have a reactive group, and may be a modified non-reactive silicone such as polyether-modified, aralkyl-modified, and long-chain alkyl-modified.
  • a commercially available product may be used, and it may be appropriately selected from various products commercially available from Shin-Etsu Silicone Co., Ltd., Toray Dow Corning, Momentive Performance Materials, and the like. If the weight average molecular weight of the reactive silicone is 14000 or more, sufficient low air permeability can be obtained.
  • the composition for polyurethane foam in the present invention may contain a crosslinking agent.
  • This crosslinking agent is preferably a bifunctional or higher functional crosslinking agent, more preferably a 2 to 6 functional crosslinking agent, still more preferably a 2 to 5 functional crosslinking agent, and a 2 to 4 functional crosslinking agent.
  • a cross-linking agent is still more preferable, and a trifunctional cross-linking agent is particularly preferable.
  • the trifunctional crosslinking agent include a trifunctional crosslinking agent having a trimethylolpropane skeleton. By using a trifunctional cross-linking agent having a trimethylol skeleton, the air permeability becomes low and the toner sealability is enhanced.
  • Examples of the functional group possessed by the trifunctional or higher functional crosslinking agent having the trimethylolpropane skeleton include a hydroxyl group, an amino group, a cyano group, an epoxy group, a carboxyl group, and a formyl group. Among these, a hydroxyl group is preferable.
  • Examples of the trifunctional cross-linking agent include “DM82162” (Okabata Sangyo Co., Ltd.).
  • Examples of the trifunctional cross-linking agent having a trimethylolpropane skeleton include “Actocol (registered trademark) T880” (Mitsui Chemicals, Inc.).
  • Trimethylolpropane EO modified triacrylate "TMP" series (Miramer M3130, Miramer M3160, Miramer M3190) (manufactured by Toyo Chemicals Co., Ltd.), trimethylolpropane PO modified triacrylate (Miramer M360) (manufactured by Toyo Chemicals Co., Ltd.) Etc.
  • TMP Trimethylolpropane EO modified triacrylate
  • Miramer M360 trimethylolpropane PO modified triacrylate
  • Etc Etc.
  • the blending amount of the bifunctional or higher functional crosslinking agent, particularly the trifunctional crosslinking agent, relative to 100 parts by mass of the polyol is 0.1 to 3.0 parts by mass. It is preferable from the viewpoint of improvement.
  • the crosslinking density of the polyurethane foam is increased and the toner sealing property is increased. Will improve. Further, by using the trifunctional crosslinking agent, the reaction rate of the polyurethane foam composition is accelerated, whereby the cells of the polyurethane foam can be miniaturized and the air permeability can be lowered.
  • the composition for producing a polyurethane foam of the present invention may contain a catalyst if desired.
  • the catalyst is used for promoting a urethanization reaction between polyol and tolylene diisocyanate, a foaming reaction between water as a blowing agent and tolylene diisocyanate, and the like, and may be appropriately selected from conventionally known compounds.
  • the catalyst according to the present invention is at least one selected from amine catalysts and organometallic catalysts.
  • an amine-based catalyst can be blended as a catalyst in the polyurethane foam composition.
  • An amine catalyst may be used individually by 1 type, and may use 2 or more types together.
  • Amine-based catalysts are broadly classified into reactive amine catalysts having a functional group having reactivity with isocyanate groups and non-reactive amine catalysts having no functional group having reactivity.
  • the reactive amine catalyst is preferably an amine compound having at least one hydroxyl group, such as N, N-dimethylaminoethoxyethanol, N, N-dimethylaminohexanol, N, N-dimethylaminoethoxyethanol, monoethanolamine, Diethanolamine, triethanolamine, dimethylaminoethanol, N, N, N′-trimethylaminoethylethanolamine, N-methyl-N ′-(2-hydroxyethyl) -piperazine, and N- (2-hydroxyethyl) morpholine Is mentioned.
  • a hydroxyl group such as N, N-dimethylaminoethoxyethanol, N, N-dimethylaminohexanol, N, N-dimethylaminoethoxyethanol, monoethanolamine, Diethanolamine, triethanolamine, dimethylaminoethanol, N, N, N′-trimethylaminoethylethanolamine, N-methyl-N ′-(2-hydroxye
  • Non-reactive amine catalysts include triethylamine, tripropylamine, tributylamine, hexadecyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, diethyltriamine, N, N, N ′, N '-Tetramethylhexanediamine, N, N, N', N'-tetramethylpropanediamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine, N, N', N'-trimethylaminoethyl Examples include piperazine, N, N-dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, and triethylenediamine.
  • the compounding amount of the amine catalyst is preferably 0.1 to 0.4 parts by mass with respect to 100 parts by mass of the polyol.
  • the polyurethane foam composition of the present invention preferably contains a reactive amine catalyst when an amine-based catalyst is blended. Since reactive amines react with isocyanates, the use of reactive amines as catalysts makes it difficult for amine catalysts to vaporize, bleed out, scatter, etc. even under wet heat conditions, etc. Since the occurrence of defects can be prevented, the printing performance can be improved.
  • the composition for polyurethane foam may contain an organometallic catalyst as a catalyst.
  • an organometallic catalyst a metal salt of a carboxylic acid can be used, and examples of the metal salt include a tin salt and a bismuth salt.
  • the organometallic catalyst tin octylate (stannas octoate), bismuth octylate (bismuth octoate), tin oleate (stannas oleate), dibutyltin diacetate, dibutyltin dilaurate, dibutyltin thio Examples thereof include carboxylate, dibutyltin dimaleate, and dioctyltin thiocarboxylate.
  • the compounding amount of the organometallic catalyst is preferably 0.1 to 0.4 parts by mass with respect to 100 parts by mass of the polyol.
  • a blending amount of the organometallic catalyst within the above range is preferable because a urethane foam having an appropriate mechanical strength can be obtained without being closed or insufficiently resinated.
  • a flame retardant, a filler, a stabilizer, a colorant, a plasticizer and the like may be blended in the polyurethane foam composition according to a conventional method, if necessary.
  • a polyurethane foam (polyurethane foam) is produced by reacting and foaming each component (raw material) of the polyurethane foam composition of the present invention according to a conventional method.
  • the reaction of the raw material of the polyurethane foam is complicated, and as a main component, a urethanization reaction by addition polymerization of a polyol and a polyisocyanate, a crosslinking reaction between the reaction product and the polyisocyanate, and a polyisocyanate and a foaming agent are used. It is a foaming reaction with water.
  • a one-shot method in which a polyol, a polyisocyanate, and other components are directly reacted is preferable, and a slab foaming method in which a reaction and foaming is performed at room temperature and atmospheric pressure is preferable.
  • the slab foaming method of the present invention for example, the polyurethane foam composition mixed and stirred by the one-shot method is discharged onto a belt conveyor, and the polyurethane foam composition is at room temperature and atmospheric pressure while the belt conveyor moves. It is a method of natural foaming and curing.
  • the polyurethane foam using the polyurethane foam composition of the present invention preferably has a tensile strength measured in accordance with JIS K 6400-5: 2012 of 55 kPa or more, more preferably 70 kPa or more. Further, the elongation at break as measured in accordance with JIS K 6400-5: 2012 is preferably 80% or more, and more preferably 100% or more.
  • the compressive residual strain measured in accordance with JIS K 6400-4: 2004 is preferably 8.6% or less, more preferably 6.0% or less, and 5.0% or less. More preferably. A compression residual strain of 5.0% or less is preferable because the resilience of the polyurethane foam is increased.
  • the hysteresis loss rate measured according to JIS K 6400-2: 2012 is preferably 70% or less, more preferably 65% or less, and still more preferably 60% or less.
  • a hysteresis loss rate of 60% or less is preferable because the resilience of the polyurethane foam is improved.
  • the polyurethane foam in the present invention preferably has an apparent density of 20 to 50 kg / m 3 measured according to JIS K 6400-1: 2004.
  • the apparent density of the polyurethane foam is more preferably 20 to 40 kg / m 3 .
  • the air permeability measured at a foam thickness of 10 mm is preferably 3.0 cm 3 / cm 2 / sec or less based on the JIS L 1096: 2010 8.26.1A method (Fragile type method).
  • the air permeability is more preferably 1.5 cm 3 / cm 2 / sec or less.
  • the number of cells measured according to JIS K 6400-1: 2004 Annex 1 is preferably 40/25 mm or more, more preferably 45/25 mm or more, and 50/25 mm. It is still more preferable that it is above.
  • the air permeability is 3.0 cm 3 / cm 2 / sec or less and the number of cells is 50/25 mm or more, the toner sealability is improved.
  • the toner seal material of the present invention is formed by foaming a polyurethane foam composition to form a polyurethane foam.
  • This toner seal material is suitably used for an image forming apparatus or the like.
  • the compression residual strain is kept small for a long period of time, and the leakage of the toner is sufficiently prevented.
  • the sealing property is good, and the leakage of the toner can be sufficiently prevented by simply interposing it on the contact surface of the cartridge body and the like and compressing it appropriately. Therefore, the structure of the member such as the frame of the toner cartridge main body can be simplified, and the required resin amount can be reduced. Therefore, it is advantageous from the viewpoint of cost reduction.
  • the toner seal material of the present invention is provided, for example, between the frames of the toner cartridge main body so that the toner filled in the toner cartridge main body incorporated in a printer which is a kind of image forming apparatus does not leak to the outside. It is used intervening. Printing by this printer is performed by attaching the toner to the photosensitive drum via the developing cylinder and attaching the toner attached to the photosensitive drum to the paper by the transfer roller. In this case, the toner may leak from between the frames of the toner cartridge body, particularly when used for a long period of time. However, the toner sealant of the present invention is interposed between the frames and the like, so that the toner is sufficiently leaked. To be prevented.
  • the apparent density, elongation at break, tensile strength, compression residual strain, hysteresis loss rate, air permeability, number of cells, toner sealability, number average molecular weight and hydroxyl value are as follows. It went by. 1. Apparent density Measured according to JIS K 6400-1: 2004. 2. Elongation at break Measured according to JIS K 6400-5: 2012. 3. Tensile strength Measured according to JIS K 6400-5: 2012. 4). Compression residual strain Measured according to JIS K 6400-4: 2004. 5). Hysteresis loss rate Measured according to JIS K 6400-2: 2012. 6).
  • Isocyanate B Tolylene diisocyanate, manufactured by Mitsui Chemicals, Inc .: trade name “Cosmonate (registered trademark) T-65” [composition mass ratio (2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate) (65/35).
  • Crosslinking agent Water * Crosslinking agent A: Trifunctional crosslinking agent, manufactured by Okabata Sangyo Co., Ltd., trade name "DM82162" * Crosslinking agent B: Trifunctional crosslinking agent, manufactured by Mitsui Chemicals, Inc., trade name “Actol (registered trademark) T880” (number average molecular weight: 224, hydroxyl value: 880 mg-KOH / g) * Crosslinking agent C: Trifunctional crosslinking agent, manufactured by Toyo Chemicals Co., Ltd., trade name “Trimethylylpropane” * Crosslinking agent D: Bifunctional crosslinking agent, “Diethylene glycol, DEG” manufactured by Mitsui Chemicals, Inc.
  • Foam stabilizer A Reactive silicone foam stabilizer Carboxy-modified organosilicone, manufactured by Toray Dow Corning, trade name “CF1218” (weight average molecular weight: 14400)
  • Foam stabilizer B Silicone foam stabilizer, manufactured by Momentive Performance Materials Japan G.K., trade name “NIAX SILICON® L-5340” (weight average molecular weight: 13000)
  • Examples 1 to 20 and Comparative Example 1 The polyurethane foam raw materials shown in Table 1 were mixed and foamed at 20 ° C. under atmospheric pressure by a one-shot method and a slab foaming method to obtain 21 types of polyurethane foams. Table 1 shows the results of the above evaluation for each polyurethane foam obtained.
  • the unit of the numerical value in the blending content of the composition of Table 1 is part by mass excluding the mass ratio.
  • the toner seal materials comprising the polyurethane foams of Examples 1 to 20 ensure superior toner sealability of the polyurethane foam as compared with the toner seal materials comprising the polyurethane foam of Comparative Example 1.
  • the tensile strength of the polyurethane foam could be increased, and the compression residual strain and hysteresis loss rate could be reduced. As a result, an excellent resilience could be exhibited.
  • the polyurethane foam obtained from the polyurethane foam composition of the present invention has excellent tensile properties, compressive residual strain and hysteresis loss rate while ensuring excellent toner sealability, and excellent restorability. It is suitably used as a toner seal material for various image forming apparatuses such as photographic apparatuses.

Abstract

The present invention provides a composition for polyurethane foam, which is obtained by blending a polyol composed of a polyester polyol and a polyether polyol, tolylene diisocyanate, a foaming agent and a foam stabilizer, and which is characterized in that: the polyester polyol contains a phthalate ester polyol; and the mass composition ratio of the tolylene diisocyanate, namely (2, 4-tolylene diisocyanate)/(2, 6-tolylene diisocyanate) is from 65/35 to 70/30. This composition for polyurethane foam enables a polyurethane foam to have enhanced tensile strength and elastic recoverability, while ensuring low air permeability and excellent toner sealability.

Description

ポリウレタンフォーム用組成物Composition for polyurethane foam
　本発明は、ポリウレタンフォーム用組成物に関し、特に、ポリウレタンフォーム用組成物を発泡させて、ポリウレタンフォームを形成してなるトナーシール材に関するものである。 The present invention relates to a polyurethane foam composition, and more particularly to a toner seal material formed by foaming a polyurethane foam composition to form a polyurethane foam.
　ポリウレタンフォームは柔軟な機械特性を有し、加工性に優れているので、各種のシール材、例えば、トナーシール材や止水性シーリング材として用いられている。
　近年の電子写真技術の進歩に伴って、乾式電子写真装置等の画像形成装置においては、帯電や現像、転写、トナー供給、クリーニングなど各種用途に供される部材として、ポリウレタンフォームを用いた部材が注目されている。このようなポリウレタンフォームを用いた部材は、例えば、帯電ローラや現像ローラ、転写ローラ、トナー供給ローラ、クリーニングローラなどの弾性を有する画像形成装置用部材の形態で用いられている。 Polyurethane foam has flexible mechanical properties and is excellent in workability, so it is used as various sealing materials such as toner sealing materials and water-proof sealing materials.
With recent advances in electrophotographic technology, in an image forming apparatus such as a dry electrophotographic apparatus, a member using polyurethane foam is used as a member for various purposes such as charging, development, transfer, toner supply, and cleaning. Attention has been paid. Such a member using polyurethane foam is used in the form of a member for an image forming apparatus having elasticity such as a charging roller, a developing roller, a transfer roller, a toner supply roller, and a cleaning roller.
　各種プリンタ等の画像形成装置では、一様に帯電させた像担持体に選択的な露光を施して潜像を形成し、この潜像をトナーで顕像化し、形成されたトナー像を記録媒体に転写することにより画像が記録される。このような装置では、適時、トナーを補給しなければならないが、このトナーの補給には、像担持体、帯電器、現像器、クリーニング器等が一体化されたトナーカートリッジが用いられており、使用者がカートリッジを装置本体に着脱することにより、トナーの補給、或いは寿命となった像担持体の交換等をすることができ、メンテナンスが容易である。このプロセスカートリッジ方式は、多くの画像形成装置において採用されているが、トナーが漏出すると画像不良を生じるため、カートリッジ本体の枠体間、現像器の現像スリーブと現像枠体との隙間等の樹脂成形品の当接面などにトナーシール材が介装されている。また、クリーニング器の像担持体の端部と廃トナー留めとの隙間には、廃トナーが漏出しないように、像担持体の端部側にトナーシール材が介装されている。 In image forming apparatuses such as various printers, a uniformly charged image carrier is selectively exposed to form a latent image, the latent image is visualized with toner, and the formed toner image is recorded on a recording medium. The image is recorded by transferring the image onto the image. In such an apparatus, toner must be replenished in a timely manner. To replenish the toner, a toner cartridge in which an image carrier, a charging device, a developing device, a cleaning device and the like are integrated is used. When the user attaches / detaches the cartridge to / from the apparatus main body, the toner can be replenished or the image carrier that has reached the end of its life can be replaced, and maintenance is easy. This process cartridge system is used in many image forming apparatuses. However, if toner leaks, an image defect occurs. Therefore, a resin such as a gap between the cartridge body frames and a gap between the developing sleeve of the developing device and the developing frame body is used. A toner seal material is interposed on the contact surface of the molded product. In addition, a toner sealant is interposed on the end portion side of the image carrier so that the waste toner does not leak into the gap between the end portion of the image carrier of the cleaning device and the waste toner holder.
　また、上記ローラ部材の他にも、シーリング性に優れたポリウレタンフォームを用いた画像形成装置の内部部材として、トナー収容部や画像形成体等の周辺に貼り付けることで、部材の合わせ目等からのトナーの漏出や拡散を防止する機能を奏するトナーシール材がある。トナーシール材に用いられるポリウレタンフォームにおいては、通気性が低く、かつ、微細なセル構造を有していることが要求される。 In addition to the above roller member, as an internal member of an image forming apparatus using polyurethane foam having excellent sealing properties, it can be attached to the periphery of a toner containing portion, an image forming body, etc. There is a toner sealing material that functions to prevent leakage and diffusion of toner. A polyurethane foam used for a toner seal material is required to have a low air permeability and a fine cell structure.
　ポリウレタンフォームを用いた画像形成装置用部材に係る技術としては、例えば、特許文献１に、ポリオール、イソシアネート、触媒および整泡剤を含むポリウレタンフォーム原料を発泡させてなるトナーシール材であって、  前記ポリオールがダイマー酸ポリオールであり、前記イソシアネート中のジフェニルメタンジイソシアネートの比率が５５～７５質量％であり、前記触媒が反応性アミンを含み、かつ、前記ポリウレタンフォーム原料が、前記ポリオール１００質量部に対し、該反応性アミンを０．２～０．５質量部にて、前記整泡剤を３～５質量部にて、それぞれ含むことを特徴とするトナーシール材が開示されている。これにより、良好なトナーシール性能を有するとともに、ポリウレタンフォーム用組成物の配合中のシリコーン整泡剤やアミン系触媒の付着、移行等による不良や不具合の発生のないトナーシール材を実現することが可能となっている。 As a technique related to a member for an image forming apparatus using a polyurethane foam, for example, Patent Document 1 discloses a toner seal material obtained by foaming a polyurethane foam raw material containing a polyol, an isocyanate, a catalyst, and a foam stabilizer. The polyol is a dimer acid polyol, the ratio of diphenylmethane diisocyanate in the isocyanate is 55 to 75% by mass, the catalyst contains a reactive amine, and the polyurethane foam raw material is based on 100 parts by mass of the polyol. There is disclosed a toner seal material comprising the reactive amine in an amount of 0.2 to 0.5 parts by mass and the foam stabilizer in an amount of 3 to 5 parts by mass. As a result, it is possible to realize a toner seal material that has good toner seal performance and that does not cause defects or defects due to adhesion or migration of a silicone foam stabilizer or an amine-based catalyst during blending of a polyurethane foam composition. It is possible.
特開２０１３－２９５９２号公報JP 2013-29592 A
　特許文献１に記載された発明により、通気性を低くして、優れたトナーシール性を有することができたが、ポリウレタンフォームのトナーシール材のシール性を確保しつつ、引張強さと復元性とを更に高めることが望ましい。
　従って、本発明が解決しようとする課題は、ポリウレタンフォームの優れたトナーシール性を確保しつつ、ポリウレタンフォームの引張強さを高く、圧縮残留歪及びヒステリシスロス率を小さくすることにより、優れた復元性を享受することができるポリウレタンフォーム用組成物を提供することにある。 According to the invention described in Patent Document 1, the air permeability was lowered and the toner sealability was excellent. However, while ensuring the sealability of the polyurethane foam toner sealant, It is desirable to further increase
Therefore, the problem to be solved by the present invention is to achieve excellent restoration by increasing the tensile strength of polyurethane foam and reducing the compression residual strain and hysteresis loss rate while ensuring the excellent toner sealability of polyurethane foam. An object of the present invention is to provide a polyurethane foam composition capable of enjoying the properties.
　本発明者は鋭意研究を重ねた結果、ポリオール、トリレンジイソシアネート、発泡剤、整泡剤及び架橋剤を配合してなるポリウレタンフォーム用組成物において、ポリオールの組成、トリレンジイソシアネートの組成及び架橋剤の官能性を限定することにより、上記の課題を解決し得ることを見出した。本発明は、かかる知見に基づいて完成したものである。 As a result of intensive studies, the present inventor has found that in a polyurethane foam composition comprising a polyol, tolylene diisocyanate, a foaming agent, a foam stabilizer and a crosslinking agent, the composition of the polyol, the composition of tolylene diisocyanate and the crosslinking agent. It was found that the above-mentioned problems can be solved by limiting the functionality of. The present invention has been completed based on such findings.
　すなわち本発明は、以下の［１］～［３］の発明を提供するものである。
［１］　ポリエステルポリオール及びポリエーテルポリオールからなるポリオール、トリレンジイソシアネート、発泡剤及び整泡剤を配合してなる組成物であって、該ポリエステルポリオールがフタル酸エステルポリオールを含み、該トリレンジイソシアネートの組成質量比（２，４－トリレンジイソシアネート／２，６－トリレンジイソシアネート）が（６５／３５）～（７０／３０）であることを特徴とするポリウレタンフォーム用組成物。
［２］　［１］に記載のポリウレタンフォーム用組成物を発泡させたポリウレタンフォームから形成されたトナーシール材。
［３］　［２］に記載のトナーシール材を用いた画像形成装置。 That is, the present invention provides the following inventions [1] to [3].
[1] A composition comprising a polyol composed of a polyester polyol and a polyether polyol, a tolylene diisocyanate, a foaming agent, and a foam stabilizer, the polyester polyol containing a phthalate ester polyol, A composition for polyurethane foam, wherein the compositional mass ratio (2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate) is (65/35) to (70/30).
[2] A toner sealing material formed from a polyurethane foam obtained by foaming the polyurethane foam composition according to [1].
[3] An image forming apparatus using the toner sealant according to [2].
　本発明によれば、ポリウレタンフォームの優れたトナーシール性を確保しつつ、ポリウレタンフォームの引張強さを高くすることができ、圧縮残留歪及びヒステリシスロス率を小さくすることができるので、優れた復元性を発揮し得るポリウレタンフォーム用組成物を提供することができる。 According to the present invention, it is possible to increase the tensile strength of the polyurethane foam while ensuring the excellent toner sealability of the polyurethane foam, and to reduce the compression residual strain and the hysteresis loss rate. The composition for polyurethane foam which can exhibit property can be provided.
トナーシール性の測定方法において、ポリウレタンフォームのサンプルを１０ｍｍ長さ×１０ｍｍ幅に打ち抜き内部にトナーを入れ、２枚のアクリル板間に５０％の圧縮状態で組み付けた状態を示す模式図である。FIG. 5 is a schematic view showing a state in which a polyurethane foam sample is punched out to a length of 10 mm × 10 mm width and a toner is put inside and assembled in a compressed state of 50% between two acrylic plates in a toner sealing property measuring method. トナーシール性の測定方法において、図２に示す６箇所についてトナーが浸食した部分の長さをノギスで測定してトナーの浸食度を測定することを示す模式図である。FIG. 3 is a schematic view showing that the erosion degree of the toner is measured by measuring the length of the portion where the toner is eroded at six locations shown in FIG.
　以下、本発明について詳細に説明する。
　なお、本発明において、数値限定を表す「Ａ～Ｂ」の記載は、端点であるＡ及びＢを含む数値範囲を意味する。
　また、質量部及び質量％は、重量部及び重量％とそれぞれ同義である。
　更に、本発明において、好ましい態様の組み合わせは、より好ましい態様である。 Hereinafter, the present invention will be described in detail.
In the present invention, the description of “A to B” representing numerical limitation means a numerical range including A and B as end points.
Moreover, a mass part and mass% are synonymous with a weight part and weight%, respectively.
Furthermore, in the present invention, a combination of preferred embodiments is a more preferred embodiment.
＜ポリウレタンフォーム用組成物＞
　以下、本発明のポリウレタンフォーム用組成物について説明する。
　本発明のポリウレタンフォーム用組成物は、ポリエステルポリオール及びポリエーテルポリオールからなるポリオール、トリレンジイソシアネート、発泡剤及び整泡剤を配合してなる組成物であって、ポリエステルポリオールがフタル酸エステルポリオールを含み、トリレンジイソシアネートの組成質量比（２，４－トリレンジイソシアネート／２，６－トリレンジイソシアネート）が（６５／３５）～（７０／３０）であることを特徴とする。
〔ポリオール〕
　本発明において、ポリウレタンフォーム用組成物はポリオールを含有し、ポリオールはポリエステルポリオール及びポリエーテルポリオールからなる。
　本発明のポリウレタンフォーム用組成物に含まれるポリオールは、ポリエステルポリオールとポリエーテルポリオールとの質量比（ポリエステルポリオール／ポリエーテルポリオール）が（７０／３０）～（３０／７０）であることが好ましく、質量比が（６０／４０）～（４０／６０）であることが更に好ましく、質量比が（５０／５０）であることが特に好ましい。ポリエステルポリオールとポリエーテルポリオールとの質量比が上記であると、引張強さと復元性を両立したウレタンフォームが得られるので好ましい。質量比（７０／３０）よりポリエステルポリオールの量が超えなければ、復元性の良いポリウレタンフォームが得られるので好ましく、質量比（３０／７０）よりポリエステルポリオールの量が少なくならなければ、高伸び高強度のポリウレタンフォームが得られるので好ましい。 <Polyurethane foam composition>
Hereinafter, the polyurethane foam composition of the present invention will be described.
The composition for polyurethane foam of the present invention is a composition comprising a polyol composed of polyester polyol and polyether polyol, tolylene diisocyanate, a foaming agent and a foam stabilizer, and the polyester polyol contains a phthalate ester polyol. The compositional mass ratio of tolylene diisocyanate (2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate) is (65/35) to (70/30).
[Polyol]
In the present invention, the polyurethane foam composition contains a polyol, and the polyol comprises a polyester polyol and a polyether polyol.
The polyol contained in the polyurethane foam composition of the present invention preferably has a mass ratio of polyester polyol to polyether polyol (polyester polyol / polyether polyol) of (70/30) to (30/70), The mass ratio is more preferably (60/40) to (40/60), and the mass ratio is particularly preferably (50/50). It is preferable that the mass ratio of the polyester polyol and the polyether polyol is the above because a urethane foam having both tensile strength and restorability can be obtained. If the amount of the polyester polyol does not exceed the mass ratio (70/30), a polyurethane foam having a good restorability is obtained. If the amount of the polyester polyol is not less than the mass ratio (30/70), the high elongation is high. It is preferable because a strong polyurethane foam can be obtained.
（ポリエステルポリオール）
　本発明においては、ポリエステルポリオールはフタル酸エステルポリオールを含む。フタル酸エステルポリオールを用いることにより、フタル酸エステルポリオールのエステル結合間の水素結合により、ポリウレタンフォームの引張強さ及び破断時の伸びが高くなる。また、高粘度により、ポリウレタンフォームのセルが微細化する効果も奏する。この観点から、本発明に係るポリエステルポリオールの全量がフタル酸エステルポリオールであることが好ましい。
　本発明に係るフタル酸エステルポリオールとしては、特に限定されないが、無水フタル酸（ｏ－フタル酸）、ｍ－フタル酸（イソフタル酸）、ｐ－フタル酸（テレフタル酸）及びこれらの誘導体から選択される少なくとも１種のフタル酸エステルポリオールを主成分とするポリエステルポリオールが好ましい。ここで、主成分とは、ポリエステルポリオール全量中、無水フタル酸（ｏ－フタル酸）、ｍ－フタル酸（イソフタル酸）、ｐ－フタル酸（テレフタル酸）及びこれらの誘導体から選択される少なくとも１種のフタル酸エステルポリオールが５０質量％以上含まれることをいい、好ましくは６０質量％以上含まれることをいい、より好ましくは７０質量％以上含まれることをいい、更に好ましくは８０質量％以上含まれることをいう。
　本発明に係るフタル酸エステルポリオールの水酸基価は、５０．０～６５．０ｍｇ－ＫＯＨ／ｇであることが好ましく、５４．０～５８．０ｍｇ－ＫＯＨ／ｇであることが好ましい。
　フタル酸エステルポリオールは、１種単独で使用してもよく、２種以上を併用してもよい。
　本発明において、フタル酸エステルポリオール以外に用いられるポリエステルポリオールとして、例えばマロン酸、コハク酸、アジピン酸、スベリン酸、セバシン酸、ブラシル酸等の炭素数３～２０の脂肪族ジカルボン酸、フタル酸以外の芳香族ジカルボン酸等と、エチレングリコール、ジエチレングリコール、プロピレングリコール等の炭素数１～６の脂肪族グリコール等とから重縮合して得られたポリエステルポリオールを挙げることできる。 (Polyester polyol)
In the present invention, the polyester polyol includes a phthalate ester polyol. By using the phthalate ester polyol, the tensile strength and elongation at break of the polyurethane foam are increased by hydrogen bonds between the ester bonds of the phthalate ester polyol. In addition, due to the high viscosity, the effect of miniaturizing the cells of the polyurethane foam is also achieved. From this viewpoint, it is preferable that the total amount of the polyester polyol according to the present invention is a phthalate ester polyol.
The phthalate ester polyol according to the present invention is not particularly limited, but is selected from phthalic anhydride (o-phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid) and derivatives thereof. Polyester polyols based on at least one phthalate ester polyol are preferred. Here, the main component is at least one selected from phthalic anhydride (o-phthalic acid), m-phthalic acid (isophthalic acid), p-phthalic acid (terephthalic acid) and derivatives thereof in the total amount of polyester polyol. It means that 50% by mass or more of a phthalate ester polyol is contained, preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more. It means that.
The hydroxyl value of the phthalate ester polyol according to the present invention is preferably 50.0 to 65.0 mg-KOH / g, more preferably 54.0 to 58.0 mg-KOH / g.
The phthalate ester polyol may be used alone or in combination of two or more.
In the present invention, as the polyester polyol used in addition to the phthalic ester polyol, for example, an aliphatic dicarboxylic acid having 3 to 20 carbon atoms such as malonic acid, succinic acid, adipic acid, suberic acid, sebacic acid, and brassylic acid, other than phthalic acid And polyester polyols obtained by polycondensation of these aromatic dicarboxylic acids and the like with aliphatic glycols having 1 to 6 carbon atoms such as ethylene glycol, diethylene glycol and propylene glycol.
（ポリエーテルポリオール）
　本発明におけるポリエーテルポリオールとしては、特に限定されるものではないが、反応性の観点からアルキレンオキシドの開環重合により得られるポリエーテルポリオールが好適である。このようなアルキレンオキシドとしてはプロピレンオキシド（ＰＯ）、エチレンオキシド（ＥＯ）等が挙げられ、これらは１種を単独で、又は２種以上を併用してもよい。
　また、上記ポリエーテルポリオールとしては、上記ＰＯの単独重合体、上記ＥＯの単独重合体、及びＰＯとＥＯとを共重合して得られたポリエーテルポリオールを用いることができる。なお、共重合は、ランダム共重合であっても、ブロック共重合であってもよい。
　重合開始剤としては、例えばペンタエリスリトール、グリセリン、エチレンジアミン、マンニッヒ、トリレンジアミン、シュークロース等が挙げられる。これら重合開始剤についても１種を単独で、又は２種以上を併用してもよい。 (Polyether polyol)
Although it does not specifically limit as a polyether polyol in this invention, The polyether polyol obtained by the ring-opening polymerization of alkylene oxide from a reactive viewpoint is suitable. Examples of such alkylene oxides include propylene oxide (PO) and ethylene oxide (EO). These may be used alone or in combination of two or more.
As the polyether polyol, the PO homopolymer, the EO homopolymer, and the polyether polyol obtained by copolymerization of PO and EO can be used. The copolymerization may be random copolymerization or block copolymerization.
Examples of the polymerization initiator include pentaerythritol, glycerin, ethylenediamine, Mannich, tolylenediamine, and sucrose. These polymerization initiators may be used alone or in combination of two or more.
〔トリレンジイソシアネート〕
　本発明は、イソシアネート化合物として、トリレンジイソシアネートを用いるものであり、イソシアネート化合物として、トリレンジイソシアネートのみを用いることが好ましい。
　このトリレンジイソシアネートの組成質量比（２，４－トリレンジイソシアネート／２，６－トリレンジイソシアネート）は（６５／３５）～（７０／３０）であることを要する。組成質量比がこの範囲であれば、ポリウレタンフォームが高伸び高強度を示すと同時に、復元性が向上する。さらに、トリレンジイソシアネートの組成質量比（７０／３０）より２，６－トリレンジイソシアネートの量が少なくならなければ、安定した発泡性を維持できるので好ましく、（６５／３５）より２，６－トリレンジイソシアネートの量が多くならなければ、得られるポリウレタンフォームのセルを微細化することができ、良好なシール性能が確保できるので好ましい。
　（２，４－トリレンジイソシアネート／２，６－トリレンジイソシアネート）が（６５未満／３５超）の場合、２，６－トリレンジイソシアネートの分子構造による影響により、泡化速度と樹脂化速度のバランスが崩れ、ウレタンフォームのセル数が５０個未満／２５ｍｍになってしまう。その為、シール性が十分に得られないので好ましくない。また、（２，４－トリレンジイソシアネート／２，６－トリレンジイソシアネート）が（７０超／３０未満）の場合、２，６－トリレンジイソシアネートが少なすぎるため、泡化速度と樹脂化速度のバランスが崩れてしまう。その為、ポリウレタンフォームを発泡成形することが困難になるので、好ましくない。
　本発明において、トリレンジイソシアネートのイソシアネート指数（イソシアネートインデックス）は１００以下又は１００を超えてもよいが、９０～１１０であることが好ましい。イソシアネート指数がこの範囲であれば、得られる発泡体の硬さが適切であり、圧縮残留歪等の機械的物性に優れる。ここで、イソシアネート指数は、ポリオール、発泡剤としての水等のもつ活性水素基に対するポリイソシアネートのイソシアネート基の当量比を百分率で表したものである。従って、イソシアネート指数が１００を越えるということは、ポリイソシアネートがポリオール等より過剰であることを意味する。 [Tolylene diisocyanate]
In the present invention, tolylene diisocyanate is used as the isocyanate compound, and it is preferable to use only tolylene diisocyanate as the isocyanate compound.
The compositional mass ratio (2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate) of tolylene diisocyanate needs to be (65/35) to (70/30). When the composition mass ratio is within this range, the polyurethane foam exhibits high elongation and high strength, and at the same time, the restorability is improved. Further, if the amount of 2,6-tolylene diisocyanate is not smaller than the compositional mass ratio (70/30) of tolylene diisocyanate, it is preferable because stable foamability can be maintained. If the amount of tolylene diisocyanate is not increased, the cells of the obtained polyurethane foam can be miniaturized, and good sealing performance can be secured, which is preferable.
When (2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate) is (less than 65 / more than 35), the foaming rate and the resinification rate are affected by the molecular structure of 2,6-tolylene diisocyanate. The balance is lost, and the number of urethane foam cells is less than 50/25 mm. Therefore, it is not preferable because sufficient sealing performance cannot be obtained. In addition, when (2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate) is (over 70 / less than 30), since 2,6-tolylene diisocyanate is too small, the foaming speed and the resinification speed are reduced. The balance will be lost. For this reason, it is difficult to foam-mold polyurethane foam, which is not preferable.
In the present invention, the isocyanate index (isocyanate index) of tolylene diisocyanate may be 100 or less or more than 100, but is preferably 90 to 110. If the isocyanate index is within this range, the resulting foam has an appropriate hardness and is excellent in mechanical properties such as compression residual strain. Here, the isocyanate index represents the equivalent ratio of the isocyanate group of the polyisocyanate to the active hydrogen group of water such as polyol and foaming agent, expressed as a percentage. Accordingly, an isocyanate index exceeding 100 means that the polyisocyanate is in excess of the polyol or the like.
〔発泡剤〕
　本発明のポリウレタンフォーム用組成物は、発泡剤を含有する。発泡剤は、ポリウレタン樹脂を発泡させて、ポリウレタンフォームとするためのものである。本発明においては、発泡剤が水を含むことが好ましく、発泡剤が水のみからなることが更に好ましい。水の配合量は、ポリオール１００質量部に対して、２．５～５．０質量部であることが好ましい。水の配合量が上記範囲内であると、泡化反応による発泡が適度に生じ、密度の低いトナーシール材が得られる。 [Foaming agent]
The polyurethane foam composition of the present invention contains a foaming agent. The foaming agent is for foaming a polyurethane resin to form a polyurethane foam. In the present invention, the foaming agent preferably contains water, and more preferably the foaming agent consists only of water. The blending amount of water is preferably 2.5 to 5.0 parts by mass with respect to 100 parts by mass of the polyol. When the blending amount of water is within the above range, foaming due to foaming reaction occurs moderately, and a toner seal material having a low density can be obtained.
〔整泡剤〕
　本発明のポリウレタンフォーム製造用組成物は、整泡剤を含有する。整泡剤は、発泡剤によって行われる発泡を円滑に進行させるために必要に応じて用いられる。そのような整泡剤としては、軟質ポリウレタン発泡体を製造する際に通常使用されるものを用いることができる。整泡剤として具体的には、シリコーン化合物、ドデシルベンゼンスルホン酸ナトリウム、ラウリル硫酸ナトリウム等のアニオン系界面活性剤、ポリエーテルシロキサン、フェノール系化合物等が用いられる。シリコーン化合物は、整泡力が高く、ポリウレタンフォームのセルを微細化し、通気性を低くするので、シリコーン系整泡剤として好適に用いられる。
　この整泡剤の配合量は、ポリオール１００質量に対して１．０～５．０質量部であることが好ましく、１．０～４．５質量部であることがより好ましく、３．５～４．５質量部であることが更に好ましい。この整泡剤の配合量が１．０質量部以上であると、発泡体原料の発泡時における整泡作用が十分に発現され微細セルかつ低通気で良好なトナーシール性を示すウレタンフォームが得られる。一方、５．０質量部以下であると、整泡作用が適当であり、発泡性を担保して所望の連通セルを有するポリウレタンフォームを得ることができる。 [Foam stabilizer]
The composition for producing a polyurethane foam of the present invention contains a foam stabilizer. The foam stabilizer is used as necessary in order to smoothly advance foaming performed by the foaming agent. As such a foam stabilizer, what is normally used when manufacturing a flexible polyurethane foam can be used. Specific examples of the foam stabilizer include silicone compounds, anionic surfactants such as sodium dodecylbenzenesulfonate and sodium lauryl sulfate, polyether siloxane, and phenolic compounds. The silicone compound has a high foam regulating power, makes the cells of the polyurethane foam fine, and lowers the air permeability. Therefore, the silicone compound is suitably used as a silicone foam regulating agent.
The blending amount of the foam stabilizer is preferably 1.0 to 5.0 parts by weight, more preferably 1.0 to 4.5 parts by weight, and more preferably 3.5 to More preferably, it is 4.5 parts by mass. When the blending amount of the foam stabilizer is 1.0 part by mass or more, a foam foam that exhibits a sufficient foam regulating action during foaming of the foam raw material and exhibits good toner sealability with fine cells and low airflow is obtained. It is done. On the other hand, if it is 5.0 parts by mass or less, the foam regulating action is appropriate, and a polyurethane foam having a desired communication cell can be obtained while ensuring foamability.
　本発明において、ポリウレタンフォーム用組成物は、反応性シリコーン整泡剤を配合することが好ましい。反応性シリコーン整泡剤を配合することにより、シリコーンがイソシアネートやポリオールと反応して結合に組み込まれ、揮発しにくくなる。ここで、反応性シリコーン整泡剤（「反応性シリコーン」と略記されることがある。）とは、アミノ基、エポキシ基、水酸基、メルカプト基、及び、カルボキシ基よりなる群から選択される少なくとも１つの反応性基を、主鎖末端、又は、側鎖に有するシリコーン化合物（ポリシロキサン化合物）をいう。
　反応性シリコーン整泡剤は、ジメチルシリコーン、メチルフェニルシリコーン、又は、メチルハイドロジェンシリコーン等のシリコーン化合物の側鎖又は主鎖末端に、アミノ基、エポキシ基、水酸基、メルカプト基、及び、カルボキシよりなる群から選択される反応性基、又は、前記反応性基を有する基を導入した化合物から選ばれることが好ましい。これらの中で、反応性基として水酸基又はカルボキシ基を有する反応性シリコーンがより好ましく、カルボキシ基を有する反応性シリコーンが更に好ましい。
　反応性シリコーン整泡剤としては、市販されている製品を使用してもよく、信越シリコーン（株）、東レダウコーニング社、モメンティブパフォーマンスマテリアルズ社などの各社製の各種反応性シリコーンが例示され、具体的には、カルボキシ基を有する反応性シリコーンとしては、ＣＦ１２１８（東レダウコーニング社製）、Ｘ２２－３７０１（信越シリコーン（株）製）が例示される。また、水酸基を有する反応性シリコーンとしては、ＳＦ　８４２７、ＢＹ　１６－２０１、ＳＦ　８４２８（以上、東レダウコーニング社製）、Ｘ－２２－４０３９、Ｘ－２２－４０１５（以上、信越シリコーン（株）製）が例示される。
　本発明において、ポリウレタンフォーム用組成物は、上記反応性シリコーンに加え、非反応性シリコーンを含有してもよいし、上記反応性シリコーンを用いず、非反応性シリコーンのみを用いてもよい。非反応性シリコーンは、反応性基を有していない限り特に限定はなく、ポリエーテル変性、アラルキル変性、長鎖アルキル変性等の変性非反応性シリコーンであってもよい。非反応性シリコーンとしては、市販されている製品を使用してもよく、信越シリコーン（株）、東レダウコーニング社、モメンティブパフォーマンスマテリアルズ社などから市販されている各種製品から適宜選択すればよい。
　反応性シリコーンの重量平均分子量は１４０００以上であれば、十分な低通気化が得られる。 In the present invention, the polyurethane foam composition preferably contains a reactive silicone foam stabilizer. By blending the reactive silicone foam stabilizer, the silicone reacts with the isocyanate or polyol and is incorporated into the bond, making it difficult to volatilize. Here, the reactive silicone foam stabilizer (sometimes abbreviated as “reactive silicone”) is at least selected from the group consisting of an amino group, an epoxy group, a hydroxyl group, a mercapto group, and a carboxy group. A silicone compound (polysiloxane compound) having one reactive group at the end of the main chain or at the side chain.
The reactive silicone foam stabilizer is composed of an amino group, an epoxy group, a hydroxyl group, a mercapto group, and carboxy at the side chain or main chain terminal of a silicone compound such as dimethyl silicone, methyl phenyl silicone, or methyl hydrogen silicone. It is preferably selected from a reactive group selected from the group or a compound into which a group having the reactive group is introduced. Among these, a reactive silicone having a hydroxyl group or a carboxy group as a reactive group is more preferable, and a reactive silicone having a carboxy group is still more preferable.
As the reactive silicone foam stabilizer, commercially available products may be used, and various reactive silicones manufactured by various companies such as Shin-Etsu Silicone Co., Ltd., Toray Dow Corning, Momentive Performance Materials, Specifically, examples of the reactive silicone having a carboxy group include CF1218 (manufactured by Toray Dow Corning) and X22-3701 (manufactured by Shin-Etsu Silicone Co., Ltd.). Examples of the reactive silicone having a hydroxyl group include SF 8427, BY 16-201, SF 8428 (above, manufactured by Toray Dow Corning), X-22-4039, X-22-4015 (above, Shin-Etsu Silicone Co., Ltd.) Manufactured).
In the present invention, the polyurethane foam composition may contain non-reactive silicone in addition to the reactive silicone, or may use only the non-reactive silicone without using the reactive silicone. The non-reactive silicone is not particularly limited as long as it does not have a reactive group, and may be a modified non-reactive silicone such as polyether-modified, aralkyl-modified, and long-chain alkyl-modified. As the non-reactive silicone, a commercially available product may be used, and it may be appropriately selected from various products commercially available from Shin-Etsu Silicone Co., Ltd., Toray Dow Corning, Momentive Performance Materials, and the like.
If the weight average molecular weight of the reactive silicone is 14000 or more, sufficient low air permeability can be obtained.
〔架橋剤〕
　本発明におけるポリウレタンフォーム用組成物には、所望により架橋剤を配合してもよい。この架橋剤は、２官能以上の架橋剤であることが好ましく、２～６官能の架橋剤であることがより好ましく、２～５官能の架橋剤であることが更に好ましく、２～４官能の架橋剤であることがより更に好ましく、３官能架橋剤であることが特に好ましい。３官能架橋剤としては、例えば、トリメチロールプロパン骨格を有する３官能架橋剤が挙げられる。トリメチロール骨格を有する３官能架橋剤を使用することにより、低通気になり、トナーシール性が高まる。
　前記トリメチロールプロパン骨格を有する３官能以上の架橋剤が有する官能基としては、例えばヒドロキシル基、アミノ基、シアノ基、エポキシ基、カルボキシル基、ホルミル基等が挙げられ、これらの中でも、ヒドロキシル基が好ましい。
　３官能架橋剤としては、例えば、「ＤＭ８２１６２」（岡畑産業株式会社）等が挙げられ、トリメチロールプロパン骨格を有する３官能架橋剤としては、「アクトコール（登録商標）Ｔ８８０」（三井化学株式会社製）、トリメチロールプロパンＥＯ変性トリアクリレート「ＴＭＰ」シリーズ（Miramer M3130、Miramer M3160、Miramer M3190）（東洋ケミカルズ株式会社製）、トリメチロールプロパンＰＯ変性トリアクリレート（Miramer M360）（東洋ケミカルズ株式会社製）等が挙げられる。
　本発明のポリウレタンフォーム用組成物において、前記ポリオール１００質量部に対する前記２官能以上の架橋剤、特に前記３官能架橋剤、の配合量が０．１～３．０質量部であることが復元性向上の観点から好ましい。ポリオール１００質量部に対して０．１～３．０質量部の範囲で２官能以上の架橋剤、特に前記３官能架橋剤、を配合することによって、ポリウレタンフォームの架橋密度が高まり、トナーシール性が向上する。また、前記３官能架橋剤を用いることにより、ポリウレタンフォーム用組成物の反応速度が加速され、これにより、ポリウレタンフォームのセルを微細化、通気性を低くすることができる。 [Crosslinking agent]
If desired, the composition for polyurethane foam in the present invention may contain a crosslinking agent. This crosslinking agent is preferably a bifunctional or higher functional crosslinking agent, more preferably a 2 to 6 functional crosslinking agent, still more preferably a 2 to 5 functional crosslinking agent, and a 2 to 4 functional crosslinking agent. A cross-linking agent is still more preferable, and a trifunctional cross-linking agent is particularly preferable. Examples of the trifunctional crosslinking agent include a trifunctional crosslinking agent having a trimethylolpropane skeleton. By using a trifunctional cross-linking agent having a trimethylol skeleton, the air permeability becomes low and the toner sealability is enhanced.
Examples of the functional group possessed by the trifunctional or higher functional crosslinking agent having the trimethylolpropane skeleton include a hydroxyl group, an amino group, a cyano group, an epoxy group, a carboxyl group, and a formyl group. Among these, a hydroxyl group is preferable.
Examples of the trifunctional cross-linking agent include “DM82162” (Okabata Sangyo Co., Ltd.). Examples of the trifunctional cross-linking agent having a trimethylolpropane skeleton include “Actocol (registered trademark) T880” (Mitsui Chemicals, Inc.). ), Trimethylolpropane EO modified triacrylate "TMP" series (Miramer M3130, Miramer M3160, Miramer M3190) (manufactured by Toyo Chemicals Co., Ltd.), trimethylolpropane PO modified triacrylate (Miramer M360) (manufactured by Toyo Chemicals Co., Ltd.) Etc.
In the polyurethane foam composition of the present invention, it is possible that the blending amount of the bifunctional or higher functional crosslinking agent, particularly the trifunctional crosslinking agent, relative to 100 parts by mass of the polyol is 0.1 to 3.0 parts by mass. It is preferable from the viewpoint of improvement. By blending a bifunctional or higher functional crosslinking agent, particularly the trifunctional crosslinking agent in the range of 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the polyol, the crosslinking density of the polyurethane foam is increased and the toner sealing property is increased. Will improve. Further, by using the trifunctional crosslinking agent, the reaction rate of the polyurethane foam composition is accelerated, whereby the cells of the polyurethane foam can be miniaturized and the air permeability can be lowered.
〔触媒〕
　本発明のポリウレタンフォーム製造用組成物は、所望により触媒を含有してもよい。触媒はポリオールとトリレンジイソシアネートとのウレタン化反応、発泡剤としての水とトリレンジイソシアネートとの泡化反応などを促進するためのものであり、従来公知の化合物から、適宜選択すればよい。本発明に係る触媒は、アミン系触媒及び有機金属触媒から１種以上選ばれる。 〔catalyst〕
The composition for producing a polyurethane foam of the present invention may contain a catalyst if desired. The catalyst is used for promoting a urethanization reaction between polyol and tolylene diisocyanate, a foaming reaction between water as a blowing agent and tolylene diisocyanate, and the like, and may be appropriately selected from conventionally known compounds. The catalyst according to the present invention is at least one selected from amine catalysts and organometallic catalysts.
　本発明において、ポリウレタンフォーム用組成物が触媒としてアミン系触媒を配合することができる。アミン系触媒は１種単独で使用してもよく、２種以上を併用してもよい。
　アミン系触媒は、イソシアネート基と反応性を有する官能基を有する反応性アミン触媒と、該反応性を有する官能基を有しない非反応性アミン触媒とに大別される。
　反応性アミン触媒としては、少なくとも一つの水酸基を有するアミン化合物が好ましく、例えば、Ｎ，Ｎ－ジメチルアミノエトキシエタノール、Ｎ，Ｎ－ジメチルアミノヘキサノール、Ｎ，Ｎ－ジメチルアミノエトキシエタノール、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジメチルアミノエタノール、Ｎ，Ｎ，Ｎ'－トリメチルアミノエチルエタノールアミン、Ｎ－メチル－Ｎ'－（２－ヒドロキシエチル）－ピペラジン、及び、Ｎ－（２－ヒドロキシエチル）モルホリンが挙げられる。
　また、非反応性アミン触媒としては、トリエチルアミン、トリプロピルアミン、トリブチルアミン、ヘキサデシルジメチルアミン、Ｎ－メチルモルホリン、Ｎ－エチルモルホリン、Ｎ－オクタデシルモルホリン、ジエチルトリアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルヘキサンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルプロパンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”－ペンタメチルジエチレントリアミン、Ｎ，Ｎ’，Ｎ’－トリメチルアミノエチルピペラジン、Ｎ，Ｎ－ジメチルシクロヘキシルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルエチレンジアミン、及び、トリエチレンジアミンが挙げられる。
　本発明において、アミン系触媒の配合量が前記ポリオール１００質量部に対して０．１～０．４質量部であることが好ましい。アミン系触媒の配合量が上記範囲内であると、ウレタン化反応及び泡化反応を十分にかつバランス良く促進させることができる。
　本発明のポリウレタンフォーム用組成物は、アミン系触媒を配合する場合は、反応性アミン触媒を含有することが好ましい。反応性アミンはイソシアネートと反応するので、触媒として反応性アミンを用いることにより、湿熱条件下等であってもアミン触媒の気化やブリードアウト、飛散等が生じにくくなり、これにより触媒成分の付着による不具合の発生を防止できるので、印字性能を向上することが可能となる。 In the present invention, an amine-based catalyst can be blended as a catalyst in the polyurethane foam composition. An amine catalyst may be used individually by 1 type, and may use 2 or more types together.
Amine-based catalysts are broadly classified into reactive amine catalysts having a functional group having reactivity with isocyanate groups and non-reactive amine catalysts having no functional group having reactivity.
The reactive amine catalyst is preferably an amine compound having at least one hydroxyl group, such as N, N-dimethylaminoethoxyethanol, N, N-dimethylaminohexanol, N, N-dimethylaminoethoxyethanol, monoethanolamine, Diethanolamine, triethanolamine, dimethylaminoethanol, N, N, N′-trimethylaminoethylethanolamine, N-methyl-N ′-(2-hydroxyethyl) -piperazine, and N- (2-hydroxyethyl) morpholine Is mentioned.
Non-reactive amine catalysts include triethylamine, tripropylamine, tributylamine, hexadecyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, diethyltriamine, N, N, N ′, N '-Tetramethylhexanediamine, N, N, N', N'-tetramethylpropanediamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine, N, N', N'-trimethylaminoethyl Examples include piperazine, N, N-dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, and triethylenediamine.
In the present invention, the compounding amount of the amine catalyst is preferably 0.1 to 0.4 parts by mass with respect to 100 parts by mass of the polyol. When the compounding amount of the amine catalyst is within the above range, the urethanization reaction and the foaming reaction can be promoted sufficiently and in a well-balanced manner.
The polyurethane foam composition of the present invention preferably contains a reactive amine catalyst when an amine-based catalyst is blended. Since reactive amines react with isocyanates, the use of reactive amines as catalysts makes it difficult for amine catalysts to vaporize, bleed out, scatter, etc. even under wet heat conditions, etc. Since the occurrence of defects can be prevented, the printing performance can be improved.
　本発明において、ポリウレタンフォーム用組成物が触媒として有機金属触媒を配合してもよい。有機金属触媒としては、カルボン酸の金属塩等を用いることができ、該金属塩としてはスズ塩やビスマス塩等が挙げられる。有機金属触媒としては、より具体的には、オクチル酸スズ（スタナスオクトエート）、オクチル酸ビスマス（ビスマスオクトエート）、オレイン酸スズ（スタナスオレエート）、ジブチルスズジアセテート、ジブチルスズジラウレート、ジブチルスズチオカルボキシレート、ジブチルスズジマレエート、ジオクチルスズチオカルボキシレート等が挙げられる。
　有機金属触媒の配合量は、ポリオール１００質量部に対して０．１～０．４質量部であることが好ましい。有機金属触媒の配合量が上記範囲内であると、独泡または樹脂化不足になることなく、適正な機械強度を持つウレタンフォームが得られるので好ましい。 In the present invention, the composition for polyurethane foam may contain an organometallic catalyst as a catalyst. As the organic metal catalyst, a metal salt of a carboxylic acid can be used, and examples of the metal salt include a tin salt and a bismuth salt. More specifically, as the organometallic catalyst, tin octylate (stannas octoate), bismuth octylate (bismuth octoate), tin oleate (stannas oleate), dibutyltin diacetate, dibutyltin dilaurate, dibutyltin thio Examples thereof include carboxylate, dibutyltin dimaleate, and dioctyltin thiocarboxylate.
The compounding amount of the organometallic catalyst is preferably 0.1 to 0.4 parts by mass with respect to 100 parts by mass of the polyol. A blending amount of the organometallic catalyst within the above range is preferable because a urethane foam having an appropriate mechanical strength can be obtained without being closed or insufficiently resinated.
〔その他の原料成分〕
　ポリウレタンフォーム用組成物にはその他必要に応じて、難燃剤、充填剤、安定剤、着色剤、可塑剤等を常法に従って配合してもよい。 [Other ingredients]
In addition, a flame retardant, a filler, a stabilizer, a colorant, a plasticizer and the like may be blended in the polyurethane foam composition according to a conventional method, if necessary.
＜ポリウレタンフォームの製造＞
　本発明のポリウレタンフォーム用組成物の各成分（原料）を常法に従って反応及び発泡させることによりポリウレタンフォーム（ポリウレタン発泡体）が製造される。
　ポリウレタンフォームの原料の反応は複雑であり、主体としては、ポリオールとポリイソシアネートとの付加重合によるウレタン化反応、その反応生成物等とポリイソシアネート類との架橋反応及びポリイソシアネート類と発泡剤としての水との泡化反応である。
　ポリウレタンフォームを製造する場合には、ポリオールとポリイソシアネートと、その他の成分を直接反応させるワンショット法が好ましく、常温大気圧下に反応及び発泡させるスラブ発泡法が好ましい。
　本発明におけるスラブ発泡法は、例えば、ワンショット法により混合撹拌されたポリウレタンフォーム用組成物をベルトコンベアに吐出し、該ベルトコンベアが移動す間にポリウレタンフォーム用組成物が常温及び大気圧下で自然発泡して硬化する方法である。 <Manufacture of polyurethane foam>
A polyurethane foam (polyurethane foam) is produced by reacting and foaming each component (raw material) of the polyurethane foam composition of the present invention according to a conventional method.
The reaction of the raw material of the polyurethane foam is complicated, and as a main component, a urethanization reaction by addition polymerization of a polyol and a polyisocyanate, a crosslinking reaction between the reaction product and the polyisocyanate, and a polyisocyanate and a foaming agent are used. It is a foaming reaction with water.
When producing a polyurethane foam, a one-shot method in which a polyol, a polyisocyanate, and other components are directly reacted is preferable, and a slab foaming method in which a reaction and foaming is performed at room temperature and atmospheric pressure is preferable.
In the slab foaming method of the present invention, for example, the polyurethane foam composition mixed and stirred by the one-shot method is discharged onto a belt conveyor, and the polyurethane foam composition is at room temperature and atmospheric pressure while the belt conveyor moves. It is a method of natural foaming and curing.
（ポリウレタンフォーム）
　本発明のポリウレタンフォーム用組成物を用いたポリウレタンフォームは、ＪＩＳ　Ｋ　６４００－５：２０１２に準拠して測定される引張強さが５５ｋＰａ以上であることが好ましく、７０ｋＰａ以上であることがより好ましい。
　また、ＪＩＳ　Ｋ　６４００－５：２０１２に準拠して測定される破断時の伸びが８０％以上であることが好ましく、１００％以上であることがより好ましい。
　そして、ＪＩＳ　Ｋ　６４００－４：２００４に準拠して測定される圧縮残留歪が８．６％以下であることが好ましく、６．０％以下であることがより好ましく、５．０％以下であることが更に好ましい。圧縮残留歪が５．０％以下であると、ポリウレタンフォームの復元性が高くなり好ましい。
　更に、ＪＩＳ　Ｋ　６４００－２：２０１２に準拠して測定されるヒステリシスロス率が７０％以下であることが好ましく、６５％以下であることが好ましく、６０％以下であることが更に好ましい。ヒステリシスロス率が６０％以下であると、ポリウレタンフォームの復元性が向上するので好ましい。 (Polyurethane foam)
The polyurethane foam using the polyurethane foam composition of the present invention preferably has a tensile strength measured in accordance with JIS K 6400-5: 2012 of 55 kPa or more, more preferably 70 kPa or more.
Further, the elongation at break as measured in accordance with JIS K 6400-5: 2012 is preferably 80% or more, and more preferably 100% or more.
The compressive residual strain measured in accordance with JIS K 6400-4: 2004 is preferably 8.6% or less, more preferably 6.0% or less, and 5.0% or less. More preferably. A compression residual strain of 5.0% or less is preferable because the resilience of the polyurethane foam is increased.
Furthermore, the hysteresis loss rate measured according to JIS K 6400-2: 2012 is preferably 70% or less, more preferably 65% or less, and still more preferably 60% or less. A hysteresis loss rate of 60% or less is preferable because the resilience of the polyurethane foam is improved.
　本発明におけるポリウレタンフォームは、ＪＩＳ　Ｋ　６４００－１：２００４に準拠して測定される見掛け密度が２０～５０ｋｇ／ｍ３であることが好ましい。この見掛け密度が２０ｋｇ／ｍ３以上であると、ポリウレタンフォームの機械的強度に優れる。その一方、見掛け密度が５０ｋｇ／ｍ３以下であると、軽量となる。
　ポリウレタンフォームの見掛け密度は、２０～４０ｋｇ／ｍ３であることがより好ましい。
　また、ＪＩＳ　Ｌ　１０９６：２０１０　８．２６．１Ａ法（フラジール型法）に準拠し、フォーム厚み１０ｍｍにて測定した通気性が３．０ｃｍ３／ｃｍ２／ｓｅｃ以下であることが好ましい。通気性が３．０ｃｍ３／ｃｍ２／ｓｅｃ以下であると、トナーシール性が向上する。通気性は、１．５ｃｍ３／ｃｍ２／ｓｅｃ以下であることがより好ましい。 The polyurethane foam in the present invention preferably has an apparent density of 20 to 50 kg / m 3 measured according to JIS K 6400-1: 2004. When the apparent density is 20 kg / m 3 or more, the mechanical strength of the polyurethane foam is excellent. On the other hand, when the apparent density is 50 kg / m 3 or less, the weight is reduced.
The apparent density of the polyurethane foam is more preferably 20 to 40 kg / m 3 .
Further, the air permeability measured at a foam thickness of 10 mm is preferably 3.0 cm 3 / cm 2 / sec or less based on the JIS L 1096: 2010 8.26.1A method (Fragile type method). When the air permeability is 3.0 cm 3 / cm 2 / sec or less, the toner sealability is improved. The air permeability is more preferably 1.5 cm 3 / cm 2 / sec or less.
　更に、ＪＩＳ　Ｋ　６４００－１：２００４　付属書１　に準拠して測定されるセル数は、４０個／２５ｍｍ以上であることが好ましく、４５個／２５ｍｍ以上であることがより好ましく、５０個／２５ｍｍ以上であることが更に好ましい。通気性が３．０ｃｍ３／ｃｍ２／ｓｅｃ以下であり、かつセル数が５０個／２５ｍｍ以上であると、トナーシール性が向上する。 Further, the number of cells measured according to JIS K 6400-1: 2004 Annex 1 is preferably 40/25 mm or more, more preferably 45/25 mm or more, and 50/25 mm. It is still more preferable that it is above. When the air permeability is 3.0 cm 3 / cm 2 / sec or less and the number of cells is 50/25 mm or more, the toner sealability is improved.
＜トナーシール材＞
　本発明のトナーシール材は、ポリウレタンフォーム用組成物を発泡させて、ポリウレタンフォームを形成してなる。このトナーシール材は画像形成装置等に好適に用いられる。
　本発明のポリウレタンフォーム用組成物を用いてなるトナーシール材であれば、長期に渡って、圧縮残留歪が小さく維持され、トナーの漏出が十分に防止される。また、硬度が低く柔軟であってもシール性が良好であり、カートリッジ本体の枠体等の当接面に介装させ、適度に圧縮させるのみでトナーの漏出を十分に防止することができる。そのため、トナーカートリッジ本体の枠体等の部材の構造を簡易なものとすることができ、所要樹脂量を低減させることもできる。従って、コストを抑えるという観点でも有利である。 <Toner sealing material>
The toner seal material of the present invention is formed by foaming a polyurethane foam composition to form a polyurethane foam. This toner seal material is suitably used for an image forming apparatus or the like.
With the toner sealing material using the polyurethane foam composition of the present invention, the compression residual strain is kept small for a long period of time, and the leakage of the toner is sufficiently prevented. Further, even if the hardness is low and flexible, the sealing property is good, and the leakage of the toner can be sufficiently prevented by simply interposing it on the contact surface of the cartridge body and the like and compressing it appropriately. Therefore, the structure of the member such as the frame of the toner cartridge main body can be simplified, and the required resin amount can be reduced. Therefore, it is advantageous from the viewpoint of cost reduction.
　本発明のトナーシール材は、例えば、画像形成装置の１種であるプリンタに組み込まれたトナーカートリッジ本体の内部に充填されたトナーが外部に漏出しないように、トナーカートリッジ本体の枠体間等に介装されて用いられる。このプリンタによる印刷は、トナーを現像シリンダを経由して感光ドラムに付着させ、感光ドラムに付着したトナーを転写ローラにより用紙に付着させることによってなされる。この場合、特に長期間用いることによりトナーカートリッジ本体の枠体間等からトナーが漏出することがあるが、枠体間等に本発明のトナーシール材を介装させることにより、トナーの漏出が十分に防止される。 The toner seal material of the present invention is provided, for example, between the frames of the toner cartridge main body so that the toner filled in the toner cartridge main body incorporated in a printer which is a kind of image forming apparatus does not leak to the outside. It is used intervening. Printing by this printer is performed by attaching the toner to the photosensitive drum via the developing cylinder and attaching the toner attached to the photosensitive drum to the paper by the transfer roller. In this case, the toner may leak from between the frames of the toner cartridge body, particularly when used for a long period of time. However, the toner sealant of the present invention is interposed between the frames and the like, so that the toner is sufficiently leaked. To be prevented.
　次に、本発明を実施例により更に詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。なお、以下の実施例及び比較例において、部及び％は、特に断りのない限り、それぞれ質量部及び質量％を意味する。 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, “part” and “%” mean “part by mass” and “mass%”, respectively, unless otherwise specified.
　以下の実施例及び比較例における、見掛け密度、破断時の伸び、引張強さ、圧縮残留歪、ヒステリシスロス率、通気性、セル数、トナーシール性、数平均分子量及び水酸基価は、以下の方法により行った。
１．見掛け密度
　ＪＩＳ　Ｋ　６４００－１：２００４に準拠して測定した。
２．破断時の伸び
　ＪＩＳ　Ｋ　６４００－５：２０１２に準拠して測定した。
３．引張強さ
　ＪＩＳ　Ｋ　６４００－５：２０１２に準拠して測定した。
４．圧縮残留歪
　ＪＩＳ　Ｋ　６４００－４：２００４に準拠して測定した。
５．ヒステリシスロス率
　ＪＩＳ　Ｋ　６４００－２：２０１２に準拠して測定した。
６．通気性
　ＪＩＳ　Ｌ　１０９６：２０１０　８．２６．１Ａ法（フラジール型法）に準拠し、フォーム厚み１０ｍｍにて測定した。
７．セル数
　ＪＩＳ　Ｋ　６４００－１：２００４　付属書１　に準拠して測定した。実体顕微鏡により観察してセル数を計測した。
８．トナーシール性
　図1に示すように、サンプルを１０ｍｍ長さ×１０ｍｍ幅に打ち抜き内部にトナーを入れ、２枚のアクリル板間に５０％の圧縮状態で組み付けた。３０分間保管後、室温にて上下各２０回振り、図２に示す６箇所についてノギスでトナーの浸食度を測定した。トナーの浸食が平均して、２．０ｍｍ以下の場合を合格とし、トナーの浸食が平均して、２．０ｍｍを超える場合を不合格とした。
９．数平均分子量
　ＧＰＣを用いて、標準ポリスチレン換算により求めた。
１０．水酸基価
　ＪＩＳ　Ｋ　１５５７－１：２００７に準拠して測定した。 In the following examples and comparative examples, the apparent density, elongation at break, tensile strength, compression residual strain, hysteresis loss rate, air permeability, number of cells, toner sealability, number average molecular weight and hydroxyl value are as follows. It went by.
1. Apparent density Measured according to JIS K 6400-1: 2004.
2. Elongation at break Measured according to JIS K 6400-5: 2012.
3. Tensile strength Measured according to JIS K 6400-5: 2012.
4). Compression residual strain Measured according to JIS K 6400-4: 2004.
5). Hysteresis loss rate Measured according to JIS K 6400-2: 2012.
6). Breathability Measured in accordance with JIS L 1096: 2010 8.26.1A method (Fragile type method) at a foam thickness of 10 mm.
7). Number of cells Measured according to JIS K 6400-1: 2004 Annex 1. The number of cells was measured by observation with a stereomicroscope.
8). Toner sealability As shown in FIG. 1, a sample was punched out to a length of 10 mm × width of 10 mm, a toner was put inside, and the sample was assembled between two acrylic plates in a compressed state of 50%. After storage for 30 minutes, each was shaken up and down 20 times at room temperature, and the erosion degree of the toner was measured with calipers at 6 locations shown in FIG. When the average erosion of the toner was 2.0 mm or less, the test was accepted. When the average erosion of the toner exceeded 2.0 mm, the test was rejected.
9. Number average molecular weight It calculated | required by standard polystyrene conversion using GPC.
10. Hydroxyl value was measured according to JIS K1557-1: 2007.
　以下の実施例及び比較例に用いられる各成分は、以下のとおりである。
＊ポリオールＡ：　フタル酸エステルポリオール、三井化学（株）製：商品名「アクトコール（登録商標）３Ｐ－５６Ｄ」（水酸基価５４．０－５８．０ｍｇ－ＫＯＨ／ｇ、粘度（２５℃）１００００－２００００ｍＰａ・ｓ）
＊ポリオールＢ：　ポリエーテルポリオール、三洋化成工業（株）製：商品名「サンニックス（登録商標）ＧＰ－３０００Ｖ」（数平均分子量：３，０００）
＊ポリオールＣ：　ポリエーテルポリオール、三洋化成工業（株）製：商品名「サンニックス（登録商標）ＧＰ－４０００Ｖ」
＊ポリオールＤ：　ダイマー酸ポリエステルポリオール、日立化成（株）製：商品名「テスラック２４５８」（数平均分子量：２５００，水酸基価：７０～７５ｍｇ－ＫＯＨ／ｇ）
＊イソシアネートＡ：　トリレンジイソシアネート、三井化学（株）製：商品名「コスモネート（登録商標）Ｔ－８０」［組成質量比（２，４－トリレンジイソシアネート／２，６－トリレンジイソシアネート）が（８０／２０）である。］
＊イソシアネートＢ：　トリレンジイソシアネート、三井化学（株）製：商品名「コスモネート（登録商標）Ｔ－６５」［組成質量比（２，４－トリレンジイソシアネート／２，６－トリレンジイソシアネート）が（６５／３５）である。］
＊イソシアネートＣ：　メチレンビス（４，１－フェニレン）＝ジイソシアネート、住化バイエルウレタン（株）製、商品名「４４Ｖ－２０Ｂ」
＊反応性アミン触媒：　エアープロダクツジャパン（株）製、商品名「ＤＡＢＣＯ（登録商標）ＮＥ３００」
＊発泡剤：　水
＊架橋剤Ａ：　３官能架橋剤、岡畑産業（株）製、商品名「ＤＭ８２１６２」
＊架橋剤Ｂ：　３官能架橋剤、三井化学（株）製、商品名「アクトコール（登録商標）Ｔ８８０」（数平均分子量：２２４、水酸基価：８８０ｍｇ－ＫＯＨ／ｇ）
＊架橋剤Ｃ：　３官能架橋剤、東洋ケミカルズ（株）製、商品名「トリメチールプロパン」
＊架橋剤Ｄ：　２官能架橋剤、三井化学（株）製「ジエチレングリコール、ＤＥＧ」
＊整泡剤Ａ：反応性シリコーン整泡剤　カルボキシ変性オルガノシリコーン、東レダウコーニング社製、商品名「ＣＦ１２１８」（重量平均分子量：１４４００）
＊整泡剤Ｂ：シリコーン整泡剤、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製、商品名「ＮＩＡＸ　ＳＩＬＩＣＯＮＥ（登録商標）Ｌ－５３４０」（重量平均分子量：１３０００） Each component used in the following examples and comparative examples is as follows.
* Polyol A: phthalate ester polyol, manufactured by Mitsui Chemicals, Inc .: trade name “Actol (registered trademark) 3P-56D” (hydroxyl value 54.0-58.0 mg-KOH / g, viscosity (25 ° C.) 10,000 -20,000 mPa · s)
* Polyol B: Polyether polyol, manufactured by Sanyo Chemical Industries, Ltd .: trade name “SANNICS (registered trademark) GP-3000V” (number average molecular weight: 3,000)
* Polyol C: Polyether polyol, manufactured by Sanyo Chemical Industries, Ltd .: Trade name “SANNICS (registered trademark) GP-4000V”
* Polyol D: Dimer acid polyester polyol, manufactured by Hitachi Chemical Co., Ltd .: Trade name “Teslac 2458” (number average molecular weight: 2500, hydroxyl value: 70 to 75 mg-KOH / g)
* Isocyanate A: Tolylene diisocyanate, manufactured by Mitsui Chemicals, Inc .: trade name “Cosmonate (registered trademark) T-80” [composition mass ratio (2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate) (80/20). ]
* Isocyanate B: Tolylene diisocyanate, manufactured by Mitsui Chemicals, Inc .: trade name “Cosmonate (registered trademark) T-65” [composition mass ratio (2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate) (65/35). ]
* Isocyanate C: Methylene bis (4,1-phenylene) = diisocyanate, manufactured by Sumika Bayer Urethane Co., Ltd., trade name “44V-20B”
* Reactive amine catalyst: Product name “DABCO (registered trademark) NE300” manufactured by Air Products Japan Co., Ltd.
* Foaming agent: Water * Crosslinking agent A: Trifunctional crosslinking agent, manufactured by Okabata Sangyo Co., Ltd., trade name "DM82162"
* Crosslinking agent B: Trifunctional crosslinking agent, manufactured by Mitsui Chemicals, Inc., trade name “Actol (registered trademark) T880” (number average molecular weight: 224, hydroxyl value: 880 mg-KOH / g)
* Crosslinking agent C: Trifunctional crosslinking agent, manufactured by Toyo Chemicals Co., Ltd., trade name “Trimethylylpropane”
* Crosslinking agent D: Bifunctional crosslinking agent, “Diethylene glycol, DEG” manufactured by Mitsui Chemicals, Inc.
* Foam stabilizer A: Reactive silicone foam stabilizer Carboxy-modified organosilicone, manufactured by Toray Dow Corning, trade name “CF1218” (weight average molecular weight: 14400)
* Foam stabilizer B: Silicone foam stabilizer, manufactured by Momentive Performance Materials Japan G.K., trade name “NIAX SILICON® L-5340” (weight average molecular weight: 13000)
実施例１～２０及び比較例１
　表１に示すポリウレタンフォーム原料を、ワンショット法及びスラブ発泡法により、大気圧下、２０℃で混合、発泡させて、２１種類のポリウレタンフォームを得た。得られた各ポリウレタンフォームにつき、上記の評価を行った結果を、表１に示す。表１の組成物の配合内容における数値の単位は、質量比を除き、質量部である。 Examples 1 to 20 and Comparative Example 1
The polyurethane foam raw materials shown in Table 1 were mixed and foamed at 20 ° C. under atmospheric pressure by a one-shot method and a slab foaming method to obtain 21 types of polyurethane foams. Table 1 shows the results of the above evaluation for each polyurethane foam obtained. The unit of the numerical value in the blending content of the composition of Table 1 is part by mass excluding the mass ratio.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から明らかなように、実施例１～２０のポリウレタンフォームからなるトナーシール材は、比較例１のポリウレタンフォームからなるトナーシール材と比較して、ポリウレタンフォームの優れたトナーシール性を確保しつつ、ポリウレタンフォームの引張強さを高くすることができ、圧縮残留歪及びヒステリシスロス率を小さくすることができた。これらにより、優れた復元性を発揮することができた。 As can be seen from Table 1, the toner seal materials comprising the polyurethane foams of Examples 1 to 20 ensure superior toner sealability of the polyurethane foam as compared with the toner seal materials comprising the polyurethane foam of Comparative Example 1. However, the tensile strength of the polyurethane foam could be increased, and the compression residual strain and hysteresis loss rate could be reduced. As a result, an excellent resilience could be exhibited.
　本発明のポリウレタンフォーム用組成物から得られるポリウレタンフォームは、優れたトナーシール性を確保しつつ、引張強さ、圧縮残留歪及びヒステリシスロス率が大幅に向上し、復元性に優れるので、乾式電子写真装置等の各種画像形成装置のトナーシール材として好適に使用される。 The polyurethane foam obtained from the polyurethane foam composition of the present invention has excellent tensile properties, compressive residual strain and hysteresis loss rate while ensuring excellent toner sealability, and excellent restorability. It is suitably used as a toner seal material for various image forming apparatuses such as photographic apparatuses.

Claims (8)

  1. 　ポリエステルポリオール及びポリエーテルポリオールからなるポリオール、トリレンジイソシアネート、発泡剤及び整泡剤を配合してなる組成物であって、該ポリエステルポリオールがフタル酸エステルポリオールを含み、該トリレンジイソシアネートの組成質量比（２，４－トリレンジイソシアネート／２，６－トリレンジイソシアネート）が（６５／３５）～（７０／３０）であることを特徴とするポリウレタンフォーム用組成物。 A composition comprising a polyol comprising a polyester polyol and a polyether polyol, a tolylene diisocyanate, a foaming agent and a foam stabilizer, wherein the polyester polyol contains a phthalate ester polyol, and the composition mass ratio of the tolylene diisocyanate A composition for polyurethane foam, wherein (2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate) is (65/35) to (70/30).
  2. 　前記ポリエステルポリオールと前記ポリエーテルポリオールとの質量比（ポリエステルポリオール／ポリエーテルポリオール）が（７０／３０）～（３０／７０）である請求項１に記載のポリウレタンフォーム用組成物。 The composition for polyurethane foam according to claim 1, wherein the mass ratio of the polyester polyol to the polyether polyol (polyester polyol / polyether polyol) is (70/30) to (30/70).
  3. 　前記整泡剤が、反応性シリコーン整泡剤を含む請求項１又は２に記載のポリウレタンフォーム用組成物。 The composition for polyurethane foam according to claim 1 or 2, wherein the foam stabilizer comprises a reactive silicone foam stabilizer.
  4. 　さらに、２官能以上の架橋剤を配合してなる請求項１～３のいずれか１項に記載のポリウレタンフォーム用組成物。 The composition for polyurethane foam according to any one of claims 1 to 3, further comprising a bifunctional or higher functional crosslinking agent.
  5. 　前記ポリオール１００質量部に対する前記２官能以上の架橋剤の配合量が０．１～３．０質量部である請求項４に記載のポリウレタンフォーム用組成物。 The composition for polyurethane foam according to claim 4, wherein the blending amount of the bifunctional or higher functional crosslinking agent with respect to 100 parts by mass of the polyol is 0.1 to 3.0 parts by mass.
  6. 　前記２官能以上の架橋剤が３官能架橋剤である請求項４又は５に記載のポリウレタンフォーム用組成物。 The polyurethane foam composition according to claim 4 or 5, wherein the bifunctional or higher functional crosslinking agent is a trifunctional crosslinking agent.
  7. 　請求項１～６のいずれか１項に記載のポリウレタンフォーム用組成物を発泡させたポリウレタンフォームから形成されたトナーシール材。 A toner seal material formed from a polyurethane foam obtained by foaming the polyurethane foam composition according to any one of claims 1 to 6.
  8. 　請求項７に記載のトナーシール材を用いた画像形成装置。 An image forming apparatus using the toner sealant according to claim 7.
PCT/JP2016/088725 2016-01-08 2016-12-26 Composition for polyurethane foam WO2017119343A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP16883842.3A EP3401345B1 (en) 2016-01-08 2016-12-26 Composition for polyurethane foam
US16/067,891 US20200262963A1 (en) 2016-01-08 2016-12-26 Composition for polyurethane foam
CN201680078086.7A CN108473656A (en) 2016-01-08 2016-12-26 Polyurethane foam composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-002590 2016-01-08
JP2016002590A JP2017122191A (en) 2016-01-08 2016-01-08 Composition for polyurethane foam

Publications (1)

Publication Number Publication Date
WO2017119343A1 true WO2017119343A1 (en) 2017-07-13

Family

ID=59274200

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/088725 WO2017119343A1 (en) 2016-01-08 2016-12-26 Composition for polyurethane foam

Country Status (5)

Country Link
US (1) US20200262963A1 (en)
EP (1) EP3401345B1 (en)
JP (1) JP2017122191A (en)
CN (1) CN108473656A (en)
WO (1) WO2017119343A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7019354B2 (en) * 2017-09-12 2022-02-15 アキレス株式会社 Laminate
WO2022224509A1 (en) * 2021-04-20 2022-10-27 株式会社イノアックコーポレーション Polyurethane foam and toner seal member

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4630309B1 (en) * 1967-03-16 1971-09-03
JPH0833095A (en) * 1994-07-20 1996-02-02 Bridgestone Corp Speaker edge material
JPH09296160A (en) * 1996-03-04 1997-11-18 Inoac Corp Polyurethane foam for sealing material and door for air conditioning apparatus using the same
JP2011121998A (en) * 2009-12-08 2011-06-23 Bridgestone Corp Polyurethane foam for frame lamination
JP2013029592A (en) 2011-07-27 2013-02-07 Bridgestone Corp Toner seal material

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4930309B1 (en) * 1966-08-31 1974-08-12
KR100479694B1 (en) * 1996-03-04 2005-07-21 가부시끼가이샤 이노아꾸 코포레이션 Polyurethane foam for sealants and doors for conditioners using it
JP4766794B2 (en) * 2001-08-07 2011-09-07 株式会社イノアックコーポレーション Flexible polyurethane foam and toner seal material using the same
JP2006028283A (en) * 2004-07-14 2006-02-02 Sakamoto Yakuhin Kogyo Co Ltd Flexible polyurethane foam and method for producing the same
JP2007016070A (en) * 2005-07-05 2007-01-25 Inoac Corp Polyurethane foam and water-stopping gasket
JP5230987B2 (en) * 2007-09-28 2013-07-10 株式会社イノアックコーポレーション Soft polyurethane foam for skin material integrated foam molding
JP2011052104A (en) * 2009-09-01 2011-03-17 Bridgestone Corp Highly flame-retardant polyurethane foam
JP5644116B2 (en) * 2010-01-21 2014-12-24 株式会社ブリヂストン High flame retardant polyurethane foam
JP5644189B2 (en) * 2010-06-03 2014-12-24 株式会社ブリヂストン High flame retardant polyurethane foam
JP5492714B2 (en) * 2010-09-09 2014-05-14 株式会社ブリヂストン Polyurethane foam

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4630309B1 (en) * 1967-03-16 1971-09-03
JPH0833095A (en) * 1994-07-20 1996-02-02 Bridgestone Corp Speaker edge material
JPH09296160A (en) * 1996-03-04 1997-11-18 Inoac Corp Polyurethane foam for sealing material and door for air conditioning apparatus using the same
JP2011121998A (en) * 2009-12-08 2011-06-23 Bridgestone Corp Polyurethane foam for frame lamination
JP2013029592A (en) 2011-07-27 2013-02-07 Bridgestone Corp Toner seal material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3401345A4

Also Published As

Publication number Publication date
CN108473656A (en) 2018-08-31
EP3401345A4 (en) 2019-01-16
EP3401345A1 (en) 2018-11-14
EP3401345B1 (en) 2020-03-25
JP2017122191A (en) 2017-07-13
US20200262963A1 (en) 2020-08-20

Similar Documents

Publication Publication Date Title
JP2011038005A (en) Manufacturing method of foamed polyurethane elastomer
JP5102991B2 (en) Toner supply roller and manufacturing method thereof
WO2017119343A1 (en) Composition for polyurethane foam
JP2010134255A (en) Toner supply roller
JP5308704B2 (en) Toner seal member
JP5367356B2 (en) Water-resistant polyurethane foam
WO2017017997A1 (en) Composition for cleaning blades for electrophotographic apparatuses and cleaning blade for electrophotographic apparatuses
JP2006308661A (en) Toner supply roller, process cartridge and image forming apparatus
JP2008033100A (en) Toner supply roller
JP6628063B2 (en) Cleaning blade
JP5046593B2 (en) Toner supply roller
JP5331037B2 (en) Soft polyurethane foam for toner seal and toner seal material using the same
JP4807870B2 (en) Toner supply roller
JP4647116B2 (en) Shape memory polyurethane foam
JP4807871B2 (en) Toner supply roller
JP4250548B2 (en) Toner supply roller
JP4509736B2 (en) Toner supply roller
JP6973747B2 (en) Water blocking material
JP3666331B2 (en) Cleaning blade
JP2006064937A (en) Toner supply roller
JP2003186366A (en) Electronic copying machine cleaning blade
JP2004099643A (en) Urethane elastomer-forming composition, method for manufacturing urethane elastomer, and urethane elastomer
JP5391113B2 (en) Soft polyurethane foam for toner seal and toner seal material using the same
JP2006153951A (en) Member for image forming apparatus
JP2007178556A (en) Toner supply roller

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16883842

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2016883842

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2016883842

Country of ref document: EP

Effective date: 20180808